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Studies of iridoid glycosides using liquid chromatography/electrospray ionization tandem mass spectrometry
Author(s) -
Ren Lingling,
Xue Xingya,
Zhang Feifang,
Wang Yongcan,
Liu Yanfang,
Li Cunman,
Liang Xinmiao
Publication year - 2007
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.3189
Subject(s) - chemistry , iridoid , tandem mass spectrometry , electrospray ionization , genipin , mass spectrometry , fragmentation (computing) , glycoside , gardenia , chromatography , organic chemistry , medicine , alternative medicine , traditional chinese medicine , pathology , chitosan , computer science , operating system
Fragmentation pathways of five iridoid glycosides have been studied by using electrospray ionization multi‐stage tandem mass spectrometry (ESI‐MS n ). The first‐stage MS data of the five iridoid glycosides were compared. The MS spectra showed that the adduct ions of iridoid glycosides and the formate anion were diagnostic ions to distinguish iridoid glycosides with a carboxyl group at the C‐4 position or an ester group at the C‐4 position. The MS fragmentation pathways of the five iridoid glycosides were also studied. Analyzing the product ion spectra of iridoid glycosides, some neutral losses were observed, such as H 2 O, CO 2 and glucose residues, which were very useful for the identification of the functional groups in the structures of iridoid glycosides. Furthermore, specific loss of one molecule of methyl 3‐oxopropanoate or 3‐oxopropanic acid was firstly discussed, which corresponded to the isomerization of the hemiacetal group in the structure of iridoid aglycone. According to the fragmentation mechanisms and HPLC/MS n data, the structures of five iridoid glycosides in a crude extract of Gardenia jasminoisdes fruit have been identified. Three compounds were compared with standards and the other two were identified as shanzhiside and genipin gentibioside by their MS n data without standard compounds. In order to further validate the veracity of the deduction, genipin gentiobioside was isolated from the extract of Gardenia jasminoisdes fruit using Purification Factory and was further identified by C‐ and H‐NMR. Copyright © 2007 John Wiley & Sons, Ltd.